Abstract
Carbon materials of different structural and textural properties (multi-walled carbon nanotubes, carbon cryogel, and carbonized hydrothermal carbon) were used as adsorbents for the removal of estrone, 17β-estradiol, and 17α-ethinylestradiol from aqueous solutions. Chemical modification and/or activation were applied to alter surface characteristics and to increase the adsorption and desorption efficiency of carbon materials. Surfaces of treated and untreated carbon materials were characterized through the examination of the textural properties, the nature of surface functional groups, and surface acidity. It was found that the adsorption capacity of tested carbon materials is not directly proportional to the specific surface area and the content of surface oxygen groups. However, a high ratio of surface mesoporosity affected the adsorption process most prominently, by increasing adsorption capacity and the rate of the adsorption process. Adsorption of estrone, 17β-estradiol, and 17α-ethinylestradiol followed pseudo-second-order kinetic model, while the equilibrium adsorption data were best fitted with the Langmuir isotherm model. Calculated mean adsorption energy values, along with the thermodynamic parameters, indicated that removal of selected hormones was dominated by the physisorption mechanism. High values of adsorption efficiency (88–100 %) and Langmuir adsorption capacities (29.45–194.7 mg/g) imply that examined materials, especially mesoporous carbon cryogel and multi-walled carbon nanotubes, can be used as powerful adsorbents for relatively fast removal of estrogen hormones from water.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Data sharing is not applicable to this article as no datasets were generated or analyzed during the current study.
References
Aharoni C, Ungarish M (1976) Kinetics of activated chemisorption. Part 1.—The non-elovichian part of the isotherm. J Chem Soc Faraday Trans 1(72):265–268. https://doi.org/10.1039/F19767200400
Akanyeti I, Kraft A, Ferrari CH (2017) Hybrid polystyrene nanoparticle-ultrafiltration system for hormone removal from water. J Water Process Eng 17:102–109. https://doi.org/10.1016/j.jwpe.2017.02.014
Ali I, Alothman ZA, Alwarthan A (2017) Supra molecular mechanism of the removal of 17-β-estradiol endocrine disturbing pollutant from water on functionalized iron nano particles. J Mol Liq 241:123–129. https://doi.org/10.1016/j.molliq.2017.06.005
Auriol M, Meknassi Y, Tyagi RD, Adams CD, Surampalli RY (2006) Endocrine disrupting compounds removal from wastewater, a new challenge. Process Biochem 41:525–539. https://doi.org/10.1016/j.procbio.2005.09.017
Auriol M, Filali-Meknassi Y, Craig DA, Tyagi RD, Noguerol TN, Piña B (2008) Removal of estrogenic activity of natural and synthetic hormones from a municipal wastewater: efficiency of horseradish peroxidase and laccase from Trametes versicolor. Chemosphere 70:445–452. https://doi.org/10.1016/j.chemosphere.2007.06.064
Barrett EP, Joyner LD, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73:373–380. https://doi.org/10.1021/ja01145a126
Barroso-Bogeat A, Alexandre-Franco M, Fernández-González C, Gómez-Serrano V (2014) FT-IR analysis of ayrone and chromene structures in activated carbon. Energy Fuel 28:4096–4103. https://doi.org/10.1021/ef5004733
Bilal M, Iqbal HMN (2019) Persistence and impact of steroidal estrogens on the environment and their laccase-assisted removal. Sci Total Environ 690:447–459. https://doi.org/10.1016/j.scitotenv.2019.07.025
Biniak S, Szymański G, Siedlewski J, Świa̧-tkowski A (1997) The characterization of activated carbons with oxygen and nitrogen surface groups. Carbon 35:1799–1810. https://doi.org/10.1016/S0008-6223(97)00096-1
Cai Y, Liu L, Tian H, Zhennai Y, Luo X (2019) Adsorption and desorption performance and mechanism of tetracycline hydrochloride by activated carbon-based adsorbents derived from sugar cane bagasse activated with ZnCl2. Molecules 24:4534. https://doi.org/10.3390/molecules24244534
Carvajal-Bernal AM, Gomez F, Giraldo L, Moreno-Pirajan JC (2015) Adsorption of phenol and 2,4-dinitrophenol on activated carbons with surface modifications. Microporous Mesoporous Mater 209:150–156. https://doi.org/10.1016/j.micromeso.2015.01.052
Celzard A, Fierro V, Amaral-Labat G (2012) Adsorption by carbon gels. In: Tascón JMD (ed) Novel Carbon Adsorbents. Elsevier, Oxford, pp 207–244. https://doi.org/10.1016/B978-0-08-097744-7.00007-7
Chen CM, Zhang Q, Yang MG, Huang CH, Yang YG, Wang MZ (2012) Structural evolution during annealing of thermally reduced graphene nanosheets for application in supercapacitors. Carbon 50:3572–3584. https://doi.org/10.1016/j.carbon.2012.03.029
Dai MY, Liu YG, Zeng GM, Liu SB, Ning QM (2019) Adsorption studies of 17β-estradiol from aqueous solution using a novel stabilized Fe–Mn binary oxide nanocomposite. Environ Sci Pollut Res 26:7614–7626. https://doi.org/10.1007/s11356-019-04173-7
Dong X, He L, Hu H, Liu N, Gao S, Piao Y (2018) Removal of 17β-estradiol by using highly adsorptive magnetic biochar nanoparticles from aqueous solution. Chem Eng J 352:371–379. https://doi.org/10.1016/j.cej.2018.07.025
Falco C, Baccile N, Titirici MM (2011) Morphological and structural differences between glucose, cellulose and lignocellulosic biomass derived hydrothermal carbons. Green Chem 13:3273–3281. https://doi.org/10.1039/c1gc15742f
Fernández L, Louvado A, Esteves VI, Gomes NCM, Almeida A, Cunha  (2017) Biodegradation of 17β-estradiol by bacteria isolated from deep sea sediments in aerobic and anaerobic media. J Hazard Mater 323:359–366. https://doi.org/10.1016/j.jhazmat.2016.05.029
Fonseca AP, Lima DLD, Esteves VI (2011) Degradation by solar radiation of estrogenic hormones monitored by UV-Visible spectroscopy and capillary electrophoresis. Water Air Soil Pollut 215:441–447. https://doi.org/10.1007/s11270-010-0489-7
Freundlich HMF (1906) Adsorption in Solution. Phys Chem 57:384–410
Gao P, Liang Z, Zhao Z, Wang W, Yang C, Hu B, Cui F (2019) Enhanced adsorption of steroid estrogens by one-pot synthesized phenyl-modified mesoporous silica: dependence on phenyl-organosilane precursors and pH condition. Chemosphere 234:438–449. https://doi.org/10.1016/j.chemosphere.2019.06.089
Gӧkce CE, Arayici S (2016) Adsorption of 17β-estradiol and estrone by activated carbon derived from sewage sludge. Desalin Water Treat 57:2503–2514. https://doi.org/10.1080/19443994.2015.1034183
Goreacioc T (2015) Oxidation and characterization of active carbon AG-5. Chem J Mold 10:76–83. https://doi.org/10.19261/cjm.2015.10(1).11
Hartmann S, Lacorn M, Steinhart H (1998) Natural occurrence of steroid hormones in food. Food Chem 62:7–20. https://doi.org/10.1016/S0308-8146(97)00150-7
Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465. https://doi.org/10.1016/S0032-9592(98)00112-5
Honorio JF, Veit MT, Suzaki PYR, Coldebella PF, Sloboda Rigobello E, Tavares CRG (2018) Adsorption of naturals hormones estrone, 17β-estradiol and estriol by rice husk: monocomponent and multicomponent kinetics and equilibrium. Environ Technol 41:1075–1092. https://doi.org/10.1080/09593330.2018.1521472
Huang T, Pan B, Ji H, Liu W (2020) Removal of 17β-estradiol by activated charcoal supported titanate nanotubes (TNTs@AC) through initial adsorption and subsequent photo-degradation: Intermediates, DFT calculation, and mechanisms. Water 12:2121. https://doi.org/10.3390/w12082121
Ifelebuegu AO (2012) Removal of steroid hormones by activated carbon adsorption—kinetic and thermodynamic studies. J Environ Prot 3:469–475. https://doi.org/10.4236/jep.2012.36057
Inyinbor AA, Adekola FA, Olatunji GA (2016) Kinetics, isotherms and thermodynamic modeling of liquid phase adsorption of rhodamine B dye onto Raphia hookerie fruit epicarp. Water Resour Ind 15:14–27. https://doi.org/10.1016/j.wri.2016.06.001
Kalijadis A, Đorđević J, Trtić-Petrović T, Vukčević M, Popović M, Maksimović V, Rakočević Z, Laušević Z (2015) Preparation of boron-doped hydrothermal carbon from glucose for carbon paste electrode. Carbon 95:42–50. https://doi.org/10.1016/j.carbon.2015.08.016
Khanal SK, Xie B, Thompson ML, Sung S, Ong SK, Van Leeuwen J (2006) Fate, transport, and biodegradation of natural estrogens in the environment and engineered systems. Environ Sci Technol 40:6537–6546. https://doi.org/10.1021/es0607739
Kumar AK, Mohan SV (2011) Endocrine disruptive synthetic estrogen (17α-ethynylestradiol) removal from aqueous phase through batch and column sorption studies: mechanistic and kinetic analysis. Desalination 276:66–74. https://doi.org/10.1016/j.desal.2011.03.022
Kumar AK, Mohan SV (2012) Removal of natural and synthetic endocrine disrupting estrogens by multi-walled carbon nanotubes (MWCNT) as adsorbent: kinetic and mechanistic evaluation. Sep Purif Technol 87:22–30. https://doi.org/10.1016/j.seppur.2011.11.015
Lagergren S (1898) Zur theorieder sogennanten adsorption geloester stoffe. Bih till K Sven Vetenskapsakademiens, Handl 24:1–39
Lalović B, Đurkić T, Vuković M, Janković-Častvan I, Kalijadis A, Laušević Z, Laušević M (2017) Solid-phase extraction of multi-class pharmaceuticals from environmental water samples onto modified multi-walled carbon nanotubes followed by LC-MS/MS. Environ Sci Pollut Res 24:20784–20793. https://doi.org/10.1007/s11356-017-9748-0
Langmuir I (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. J Am Chem Soc 40:1361–1403
Lazić BD, Pejić BM, Kramar AD, Vukčević MM, Mihajlovski KR, Rusmirović JD, Kostić MM (2018) Influence of hemicelluloses and lignin content on structure and sorption properties of flax fibers (Linum usitatissimum L.). Cellulose 25:697–709. https://doi.org/10.1007/s10570-017-1575-4
Lowell S, Shields JE, Thomas MA, Thommes M (2004) Characterization of porous solids and powders: surface area, pore size and density. Springer, Dordrecht
Luo Z, Li H, Yang Y, Lin H, Yang Z (2017) Adsorption of 17α-ethinylestradiol from aqueous solution onto a reduced graphene oxide-magnetic composite. J Taiwan Inst Chem Eng 80:797–804. https://doi.org/10.1016/j.jtice.2017.09.028
Maletić M, Vukčević M, Kalijadis A, Janković-Častvan I, Dapčević A, Laušević Z, Laušević M (2019) Hydrothermal synthesis of TiO2/carbon composites and their application for removal of organic pollutants. Arab J Chem 12:4388–4397. https://doi.org/10.1016/j.arabjc.2016.06.020
Minović TZ, Gulicovski JJ, Stoiljkovic MM, Jokic BM, Živković LS, Matovic BZ, Babić BM (2015) Surface characterization of mesoporous carbon cryogel and its application in arsenic (III) adsorption from aqueous solutions. Microporous Mesoporous Mater 201:271–276. https://doi.org/10.1016/j.micromeso.2014.09.031
Mita L, Forte M, Rossi A, Adamo C, Rossi S, Mita DG, Guida M, Portaccio M, Godievargova T, Yavour I, Samir M, Eldin M (2017) Removal of 17-α Ethinylestradiol from water systems by adsorption on polyacrylonitrile beads: isotherm and kinetics studies. Peertechz J Environ Sci Toxicol 2:48–58. https://doi.org/10.17352/pjest.000012
Patel S, Han J, Gao W (2015) Sorption of 17β-estradiol from aqueous solutions on to bone char derived from waste cattle bones: kinetics and isotherms. J Envron Chem Eng 3:1562–1569. https://doi.org/10.1016/j.jece.2015.04.027
Prokić D, Vukčević M, Kalijadis A, Maletić M, Babić B, Đurkić T (2020) Removal of estrone, 17β-estradiol, and 17α-ethinylestradiol from water by adsorption onto chemically modified activated carbon cloths. Fibers Polym 21:2263–2274. https://doi.org/10.1007/s12221-020-9758-2
Ren X, Chen C, Nagatsu M, Wang X (2011) Carbon nanotubes as adsorbents in environmental pollution management: a review. Chem Eng J 170:395–410. https://doi.org/10.1016/j.cej.2010.08.045
Rusmirović JD, Rančić MP, Pavlović VB, Rakić VM, Stevanović S, Đonlagić J, Marinković AD (2018) Cross-linkable modified nanocellulose/polyester resin-based composites: effect of unsaturated fatty acid nanocellulose modification on material performances. Macromol Mater Eng 303:1700648. https://doi.org/10.1002/mame.201700648
Sajjadi B, Zubatiuk T, Leszczynska D, Leszczynski J, Chen WY (2019) Chemical activation of biochar for energy and environmental applications: a comprehensive review. Rev Chem Eng 35:777–815. https://doi.org/10.1515/revce-2018-0003
Sevilla M, Fuertes AB (2009) The production of carbon materials by hydrothermal carbonization of cellulose. Carbon 47:2281–2289. https://doi.org/10.1016/j.carbon.2009.04.026
Silva RCF, Ardisson JD, Chaves Cotta AA, Araujo MH, Carvalho Teixeira AP (2020) Use of iron mining tailings from dams for carbon nanotubes synthesis in fluidized bed for 17α-ethinylestradiol removal. Environ Pollut 260:114099. https://doi.org/10.1016/j.envpol.2020.114099
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 57:603–619. https://doi.org/10.1351/pac198557040603
Snyder SA, Westerhoff P, Yoon Y, Sedlak DL (2004) Pharmaceuticals, personal care products, and endocrine disruptors in water: implications for the water industry. Environ Eng Sci 20:449–469. https://doi.org/10.1089/109287503768335931
Sornalingam K, McDonagh A, Zhou JL (2016) Photodegradation of estrogenic endocrine disrupting steroidal hormones in aqueous systems : progress and future challenges. Sci Total Environ 550:209–224. https://doi.org/10.1016/j.scitotenv.2016.01.086
Tagliavini M, Schäfer AI (2018) Removal of steroid micropollutants by polymer-based spherical activated carbon (PBSAC) assisted membrane Filtration. J Hazard Mater 353:514–521. https://doi.org/10.1016/j.jhazmat.2018.03.032
Tagliavini M, Engel F, Weidler PG, Scherer T, Schäfer AI (2017) Adsorption of steroid micropollutants on polymer-based spherical activated carbon (PBSAC). J Hazard Mater 337:126–137. https://doi.org/10.1016/j.jhazmat.2017.03.036
Tang P, Sun Q, Suo Z, Zhao L, Yang H, Xiong X, Pu H, Gan N, Li H (2018) Rapid and efficient removal of estrogenic pollutants from water by using beta- and gamma-cyclodextrin polymers. Chem Eng J 344:514–523. https://doi.org/10.1016/j.cej.2018.03.127
Teixeira APC, Purceno AD, de Paula CCA, da Silva JCC, Ardisson JD, Lago RM (2013) Efficient and versatile fibrous adsorbent based on magnetic amphiphilic composites of chrysotile/carbon nanostructures for the removal of ethynilestradiol. J Hazard Mater 248–249:295–302. https://doi.org/10.1016/j.jhazmat.2013.01.014
Thanhmingliana LC, Tiwari D, Lee SM (2016) Efficient removal of 17β-estradiol using hybrid clay materials: batch and column studies. Environ Eng Res 21:203–210. https://doi.org/10.4491/eer.2016.003
Vilela CLS, Bassin JP, Peixoto RS (2018) Water contamination by endocrine disruptors: Impacts, microbiological aspects and trends for environmental protection. Environ Pollut 235:546–559. https://doi.org/10.1016/j.envpol.2017.12.098
Vukčević M, Kalijadis A, Babić B, Laušević Z, Laušević M (2013) Influence of different carbon monolith preparation parameters on pesticide adsorption. J Serb Chem Soc 78:1617–1632. https://doi.org/10.2298/JSC131227006V
Wang F, Sun W, Pan W, Xu N (2015) Adsorption of sulfamethoxazole and 17β-estradiol by carbon nanotubes/CoFe2O4 composites. Chem Eng J 274:17–29. https://doi.org/10.1016/j.cej.2015.03.113
Wang X, Liu Z, Ying Z, Huo M, Yang W (2018) Adsorption of trace estrogens in ultrapure and wastewater treatment plant effluent by magnetic graphene oxide. Int J Environ Res Public Health 15:1454. https://doi.org/10.3390/ijerph15071454
Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from solutions. J Sanit Eng Div Am Soc Civil Eng 89:31–59
Yu Z, Hu C, Dichiara AB, Jiang W, Gu J (2020) Cellulose nanofibril/carbon nanomaterial hybrid aerogels for adsorption removal of cationic and anionic organic dyes. Nanomaterials 10:169. https://doi.org/10.3390/nano10010169
Zhang Y, Zhou JL (2005) Removal of estrone and 17β-estradiol from water by adsorption. Water Res 39:3991–4003. https://doi.org/10.1016/j.watres.2005.07.019
Zhang Y, Zhou JL, Ning B (2007) Photodegradation of estrone and 17β-estradiol in water. Water Res 41:19–26. https://doi.org/10.1016/j.watres.2006.09.020
Zhang H, Ming R, Yang G, Li Y, Li Q, Shao H (2015) Influence of alkali treatment on flax fiber for use as reinforcements in polylactide stereocomplex composites. Polym Eng Sci 55:2553–2558. https://doi.org/10.1002/pen.24147
Zhong S, Zhang S, Zhang Y, Li C (2019) Performance and mechanism of estrone (E1) and 17β-estradiol (17β-E2) removal from aqueous solution using hexadecyltrimethylammonium (HDTMA) modified zeolites. J Mater Sci Mater Electron 30:20410–20419. https://doi.org/10.1007/s10854-019-02375-w
Funding
The research was funded by the Ministry of Education, Science and Technological Development of the Republic of Serbia (Contract No. 451-03-9/2021-14/200135 and Contract No. 451-03-9/2021-14/200287).
Author information
Authors and Affiliations
Contributions
Conceptualization, Tatjana Đurkić; material preparation and investigation, Danijela Prokić, Angelina Mitrović, Ana Kalijadis, and Ivona Janković-Častvan; data analysis and writing-original draft, Marina Maletić and Danijela Prokić; and writing-review and editing the paper, Marija Vukčević and Tatjana Đurkić. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible editor: Tito Roberto Cadaval Jr
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
ESM 1
(DOCX 829 kb)
Rights and permissions
About this article
Cite this article
Prokić, D., Vukčević, M., Mitrović, A. et al. Adsorption of estrone, 17β-estradiol, and 17α-ethinylestradiol from water onto modified multi-walled carbon nanotubes, carbon cryogel, and carbonized hydrothermal carbon . Environ Sci Pollut Res 29, 4431–4445 (2022). https://doi.org/10.1007/s11356-021-15970-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-021-15970-4